CN112645589A - Chemically strengthened glass, preparation method of chemically strengthened glass and raw material glass - Google Patents
Chemically strengthened glass, preparation method of chemically strengthened glass and raw material glass Download PDFInfo
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- CN112645589A CN112645589A CN201911061861.XA CN201911061861A CN112645589A CN 112645589 A CN112645589 A CN 112645589A CN 201911061861 A CN201911061861 A CN 201911061861A CN 112645589 A CN112645589 A CN 112645589A
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- 239000011521 glass Substances 0.000 title claims abstract description 240
- 239000002994 raw material Substances 0.000 title claims abstract description 159
- 239000005345 chemically strengthened glass Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005342 ion exchange Methods 0.000 claims abstract description 52
- 238000002834 transmittance Methods 0.000 claims abstract description 10
- 230000003247 decreasing effect Effects 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims description 68
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 229910052593 corundum Inorganic materials 0.000 claims description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 17
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- -1 hydroxide ions Chemical class 0.000 claims description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 230000001066 destructive effect Effects 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 3
- 229910052664 nepheline Inorganic materials 0.000 claims description 3
- 239000010434 nepheline Substances 0.000 claims description 3
- 229910052670 petalite Inorganic materials 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 229910000500 β-quartz Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 description 34
- 229910001415 sodium ion Inorganic materials 0.000 description 20
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000006058 strengthened glass Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003426 chemical strengthening reaction Methods 0.000 description 5
- 239000005341 toughened glass Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006018 Li-aluminosilicate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010205 computational analysis Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses chemically strengthened glass, a preparation method of the chemically strengthened glass and raw material glass. The thickness of a compressive stress layer formed on the surface of the chemically strengthened glass through ion exchange is less than or equal to one tenth of the thickness of the glass, and the surface compressive stress is greater than or equal to 600 MPa; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has a tensile stress linear density of 20000 to 75000Mpa/mm, a thickness of 0.4 to 10mm, a Vickers hardness of more than 520HV, an average visible light transmittance of 90 to 92%, and a temperature of 1300 ℃ or less at a viscosity of lg4 (visc./(Poise)). The chemically strengthened glass has the advantages of high strength, high safety, low expansion coefficient, high transmittance and high hardness.
Description
Technical Field
The invention belongs to the technical field of glass and glass manufacturing, and particularly relates to chemically strengthened glass, a preparation method of the chemically strengthened glass and raw material glass.
Background
Ion-exchange strengthened glass is used more and more widely because of its high strength. For example, windshields of high-speed moving vehicles (especially civil aircraft, military aircraft and high-speed trains), protective cover plates of handheld electronic terminals and electric automobiles adopt strengthened glass, so that the thickness can be reduced, energy is saved, and the working mileage of batteries is prolonged.
In chemical strengthening, in order to increase the strength of glass, the common technical means is to increase the ion exchange strength to increase the surface compressive stress and deepen the depth of the compressive stress of the glass, so that the tensile stress in the central region inside the glass is also increased continuously to maintain the stress balance of the glass. At present, chemically strengthened glass is usually obtained by performing ion exchange on lithium-aluminum-silicon glass in a chemically strengthened salt bath, the compressive stress depth DOL of the chemically strengthened glass is usually more than 100um, and more internal tensile stress can be accommodated, but the internal tensile stress is increased, and the stability and safety of the glass are reduced; among all elements which can be ion exchanged, lithium ions are the smallest, so that the surface compressive stress and the surface hardness generated after ion exchange are too low, irreversible micro scratches and cracks are easy to generate, safety problems are induced, and the problems of instant strength release and complete breakage of glass are caused. In addition, in the process of ion exchange between the lithium aluminosilicate glass and the salt bath, lithium ions are the smallest among all elements capable of being ion exchanged, so that the surface compressive stress and the surface hardness generated after ion exchange are too low, irreversible micro scratches and cracks are easy to generate, safety problems are induced, and the problems of instant strength release and complete breakage of the glass are easily caused. Furthermore, after the lithium ions participate in ion exchange, the lithium ions have a great influence on the deterioration of the salt bath, and are very easy to cause salt bath poisoning, so that the stress between batches of the tempered glass is unstable and stable, and the stress at different positions on the same piece of glass is inconsistent.
Therefore, the chemically strengthened glass with high strength, high safety, low expansion coefficient, high transmittance and high hardness is designed, has single compression stress distribution with gradual decrease and gradual change, has higher destructive strength and excellent safety, and has far lower spontaneous explosion risk than the strengthened glass in the prior art.
In addition, the chemical strengthening process of the lithium-aluminum-silicon glass is usually binary ion exchange or multiple ion exchange, the process is complex and is not easy to control, the equipment occupancy rate is high, and the production cost is high. Secondly, the lithium-aluminum-silicon glass contains a large amount of Li, and although the melting stage of the glass is relatively easy, the lithium-aluminum-silicon glass has extremely high crystallization tendency and high production difficulty in the temperature operation range above 1200 ℃. Li is a rare element and also is the most important component of a lithium battery, and with the application of a large amount of new energy and batteries, the cost of Li is always increased and high, so that the manufacturing cost of the lithium-aluminum-silicon glass is very high. The invention also designs the raw material glass which is particularly suitable for obtaining the chemically strengthened glass by ion exchange, and the raw material glass has a special formula and has the advantages of low brittleness, high strength, high safety, low expansion coefficient, high wear resistance, high transmittance and lower dielectric constant.
Meanwhile, the invention also designs a preparation method which has simple and easily controlled process and low production cost and can form the chemically strengthened glass.
Disclosure of Invention
The present invention is directed to providing chemically strengthened glass having advantages of high strength, high safety, low expansion coefficient, high transmittance, and high hardness.
Another technical problem to be solved by the present invention is to provide a method for preparing chemically strengthened glass, wherein the method is a process for preparing the strengthened glass from raw material glass, and has the advantages of simple process and easy control.
Another technical problem to be solved by the present invention is to provide a raw material glass having the advantages of low brittleness, high strength, high safety, low expansion coefficient, high wear resistance, high transmittance, uniform thickness, large size, large thickness range, and low dielectric constant.
In order to solve the technical problems, the invention provides chemically strengthened glass, wherein the thickness of a compressive stress layer formed on the surface of the chemically strengthened glass through ion exchange is less than or equal to one tenth of the thickness of the glass, and the surface compressive stress is greater than or equal to 600 MPa; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has a tensile stress linear density of 20000 to 75000Mpa/mm, a thickness of 0.4 to 10mm, a Vickers hardness of more than 520HV, an average visible light transmittance of 90 to 92%, and a temperature of 1300 ℃ or less at a viscosity of lg4 (visc./(Poise)).
Preferably, the surface compressive stress of the chemically strengthened glass provided by the invention is 650 to 1100 MPa.
As the optimization of the chemically strengthened glass provided by the invention, the surface compressive stress is 700-900 MPa.
Preferably, the chemically strengthened glass provided by the invention has a tensile stress linear density of 28000-58000 MPa/mm.
Preferably, the chemically strengthened glass provided by the invention has a tensile stress linear density of 28000-50000 MPa/mm.
Preferably, in the chemically strengthened glass of the present invention, the depth of the ion exchange layer formed on the surface of the chemically strengthened glass by ion exchange is at least 20 μm greater than the depth of the compressive stress layer.
The chemical strengthening glass provided by the invention preferably has an expansion coefficient of 50 multiplied by 10 under the temperature condition of-100 to 100 DEG C-7/℃～100×10-7/℃。
Preferably, in the chemically strengthened glass provided by the present invention, in a static pressure destructive test, an area of a largest fragment formed by breaking the chemically strengthened glass having a length × width × thickness dimension of 50mm × 50mm × 0.7mm is 5% to 45% of a total area of the chemically strengthened glass subjected to the test.
In order to solve another problem of the technology, the invention also provides a preparation method of the chemically strengthened glass, which is to place the raw material glass in the mixed salt bath for ion exchange to prepare the chemically strengthened glass; the mixed salt bath contains at least three metal ions which are respectively K+、Na+、Li+Wherein, K is+The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na+The content of Li in the mixed salt bath is not less than 500ppm+The content of the salt in the mixed salt bath is 20-1000 ppm.
As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, K+Molar amount of (A)>Na+Molar amount of (A)>Li+The molar amount of (c).
As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, Na+The molar amount of (b) is 30% or less of the total molar amount of alkali metal ions.
As a preferable aspect of the production method provided by the present invention, in the mixed salt bath, Na+The molar amount of (a) is less than 25% of the total molar amount of alkali metal ions.
Preferably, in the preparation method provided by the present invention, the mixed salt bath further contains non-ionic alumina, and the non-ionic alumina accounts for 2% or less of the mass of the mixed salt bath.
As a preference of the preparation method provided by the present invention, the preparation method is a single ion exchange.
As the optimization of the preparation method provided by the invention, the ion exchange time is 3-12 hours, and the ion exchange temperature is 390-500 ℃.
Preferably, the mixed salt bath contains nitrate ion NO3 -，NO3 -The molar amount of (a) is 95% or more of the total molar amount of the anions.
Preferably, the mixed salt bath contains hydroxide ions OH-，OH-The molar amount of (a) is 2.5% or less of the total molar amount of anions.
As a preference of the preparation method provided by the present invention, the mixed salt bath further comprises other anions: CO 23 2-Or/and PO4 3-。
Preferably, in the preparation method provided by the invention, Li in the mixed salt bath+The content of (B) is 20-600 ppm.
Preferably, the mixed salt bath contains hydroxide ions OH-，OH-The molar weight of (A) is more than 1.1 percent of the total molar weight of anions
In order to solve another technical problem, the present invention further provides a raw material glass, which is processed by the above preparation method to obtain the chemically strengthened glass, wherein the raw material glass comprises the following elements in mol percentage: the raw material glass comprises the following elements in mol percentage: 3 to 11.5 percent of Na, 17 to 24 percent of Si, 5.6 to 10.5 percent of Al, 0.25 to 5 percent of Mg and 58 to 62 percent of O.
As a preferable aspect of the raw material glass provided by the invention, the raw material glass contains the following elements in mol percentage: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg, 58.52 to 61.52 percent of O and Cl and S with the total of 0.01 to 0.25 percent; wherein the content of S is 0.01-0.22%, and the ratio of Na content to Li content is 1-11.5.
As a preference of the raw material glass provided by the invention, the raw material glass contains the following oxides in mole percentage: 6 to 18 percent of Na2O, SiO 60% or more29% or more of Al2O31 to 6% of Li2O, MgO of more than or equal to 1 percent and SO of 0.01 to 0.2 percent3。
The raw material glass provided by the invention preferably has an elastic modulus of 65-88.2 Gpa and a Vickers hardness of 490-592 kgf/mm2And the brittleness is 57.5-72.3. Wherein,
the brittleness formula is defined in the special example, Vickers hardness is introduced in the formula to reflect the plastic deformation capability of the glass, and the Vickers hardness and the elastic modulus of the glass are controlled within a reasonable range although the plastic deformation capability of the glass is lower, so that the brittleness of the glass can be effectively reduced.
Preferably, the raw material glass has a dielectric constant of 5.5 to 7.75 at a frequency of 1MHZ to 3.5 GHZ.
The raw material glass provided by the invention preferably has an expansion coefficient of 57 multiplied by 10 under the temperature condition of 20-400 DEG C-7/℃～101×10-7/℃。
The raw material glass provided by the invention preferably has a density of 2.38-2.52g/cm at a temperature of 20 DEG C3。
Preferably, the raw material glass provided by the invention has a corresponding temperature of 1250-1493 ℃ when the viscosity of the raw material glass is lg3 (visc./(Poise)); the liquid line temperature is 1060-1300 ℃; the softening point temperature is 710-880 ℃; the Tg temperature of the transition point is 515-620 ℃.
As a preference of the raw material glass provided by the invention, the raw material glass further contains the following oxides in mole percentage: 0.5% -2% of ZrO2(ii) a Wherein Li2O content of 2% or more, SiO2The content of (A) is 62 to 75 percent, and Al2O39 to 17 percent of Na2Content of O and Li2The sum of the contents of O is 9 to 20 percent, and the content of MgO is 2 to 12 percent.
As a preferable aspect of the raw material glass provided by the present invention, the raw material glass contains more total alkali metal oxide than Al2O3Content of (A), Na2Content of O and Li2The ratio of the content of O is 1-9.
Preferably, the blending index theta of O and Si in the raw material glass is 0.35-1.10. Wherein the blending index
Wherein X is the ratio of the content of O to the content of Si in the raw material glass. Further, the blending index theta is 0.61-1.10, and further, the blending index theta is 0.71-1.10.
As a preference of the raw material glass provided by the invention, the raw material glass further contains the following oxides in mole percentage: 1% -4% of B2O3(ii) a Wherein the total content of alkali metal oxide and Al2O3Difference of contents of (A) and (B)2O3The absolute value of the ratio of the contents of (a) is 1 or more.
The raw material glass provided by the invention preferably has an elastic modulus of 65-77 Gpa, a dielectric constant of 5.59-7.58 under the condition that the frequency is 1 MHZ-3.5 GHZ, and a density at 20 ℃ of 2.387-2.495 g/cm3。
The raw material glass provided by the invention preferably has a corresponding temperature of 1274-1493 ℃, a liquid line temperature of 1086-1300 ℃, and a softening point temperature of 726-876 ℃ when the viscosity of the raw material glass is lg3 (visc./(Poise)).
As a preference of the raw material glass provided by the invention, the raw material glass includes an amorphous portion and a plurality of shaped portions; the size of each shaping part is 5-100 nm; the average size of all of the shaped portions is less than 50 nm; the average size of all of the shaped portions is less than 30 nm.
Preferably, the average size of all the shaped portions is 10 to 30 nm.
As the optimization of the raw material glass provided by the invention, the shaping part comprises nepheline and ZrO2One or more of cordierite, spinel, a solid solution of beta-quartz, petalite and lithium silicate.
As a preferable aspect of the raw material glass provided by the invention, Al in the raw material glass2O3The content of (a) is 9-15.5%, and the raw material glass also comprises the following oxides in percentage by mole: 0.5-2% of rare earth oxide and 0.5-4% of K2O, 0 to 7% of P2O5(ii) a Wherein the rare earth oxide at least comprises CeO2And CeO2The content of (A) is more than or equal to 0.5 percent; k2O、Na2O and Li2The sum of the contents of O is 1 to 20 percent.
The raw material glass provided by the invention preferably has an elastic modulus of 65.6-75.4 Gpa and a Vickers hardness of 510-592 kgf/mm2The expansion coefficient of the raw material glass at the temperature of 20-400 ℃ is 60 multiplied by 10-7/℃～100.3×10-7The density at 20 ℃ is 2.39-2.491 g/cm3。
Preferably, the raw material glass has a viscosity of lg3(visc./(Poise)) corresponding to a temperature of 1299 to 1493 ℃, a liquidus temperature of 1112 to 1300 ℃, a softening point temperature of 745 to 876 ℃ and a transition point Tg temperature of 515 to 579 ℃.
The raw material glass provided by the invention preferably has an elastic modulus of 67-75.4 Gpa and a density at 20 ℃ of 2.417-2.48 g/cm3。
Preferably, the brittleness of the raw material glass provided by the invention is 60-69.2.
As a preferable aspect of the raw material glass provided by the present invention, Na is contained in the raw material glass29-15.5% of O, Li2The content of O is 2-5%.
The raw material glass provided by the invention preferably has an elastic modulus of 67.2-75.4 Gpa, a brittleness of 60-68.5, a dielectric constant of 5.87-7.52 under the condition of a frequency of 1 MHZ-3.5 GHz, and an expansion coefficient of 71 x 10 under the condition of a temperature of 20-400 DEG C-7/℃～100.3×10-7The density at 20 ℃ is 2.42-2.48 g/cm3(ii) a The raw material glass has a viscosity of lg3(visc./(Poise)) corresponding to a temperature of 1330-1450 ℃, a liquidus temperature of 1130-1255 ℃, and a softening point temperature of 745-850 DEG C
In the raw material glass, preferably, Na is present in the raw material glass in a molar percentage2The content of O is 11-15.5%, and Li2The content of O is 2-5%.
The raw material glass provided by the invention is preferably 0.4-10 mm thick.
The raw material glass provided by the invention is preferably 0.4-8mm thick.
Preferably, the raw material glass provided by the invention further comprises 0.01 to 0.25% of S in mol percentage.
The raw material glass provided by the invention is preferably selected from the raw material glass, wherein the mol percentage content of S in the raw material glass is 0.01-0.22%,
the raw material glass provided by the invention is preferably selected from the raw material glass, wherein the S content in the raw material glass is 0.01-0.15% by mol.
Preferably, the size of the raw material glass is increased by 0.05 to 0.1% after the raw material glass is subjected to ion exchange treatment.
Drawings
FIG. 1 is a schematic diagram illustrating the comparison of DOI and DOL in a chemically strengthened glass according to the present invention;
FIG. 2 example 75 provides a DOI profile and a DOL profile within a chemically strengthened glass.
Detailed Description
Before describing the soda glass, the preparation method and the chemically strengthened glass, it is necessary to explain some terms and some methods for measuring physicochemical properties.
Method for measuring compressive stress value (CS): the measurements were carried out using an optical waveguide Surface Stress Meter (Orihara Surface Stress Meter, FSM6000 LE).
The detection method of the depth of layer (DOL) of the compressive stress comprises the following steps: the measurements were carried out using an optical waveguide Surface Stress Meter (Orihara Surface Stress Meter, FSM6000 LE).
The detection method of the tensile stress value (CT) comprises the following steps: after the compressive Stress distribution data of the Surface and the interior of the glass are obtained by measuring with an optical waveguide Surface Stress Meter (FSM 6000LE), the compressive Stress, the maximum tensile Stress, the average tensile Stress and the tensile Stress distribution are obtained by fitting with Orihara Pmc software.
DOI indicates the depth of penetration of alkali metal ions into the glass due to the ion exchange process and can be determined by Electron Probe Microanalysis (EPMA) or glow discharge-optical emission spectroscopy (GD-OES). The DOI of the chemically strengthened glass provided by the present invention is generally much greater than DOL.
Tensile stress linear density: the strengthened glass is formed by ion exchange in salt bath, a stress layer is formed in the glass during the ion exchange process, the tensile Stress layer is provided with an upper boundary which is at a certain interval with the upper Surface of the tempered glass and a lower boundary which is at a certain interval with the lower Surface of the tempered glass, a curve which is drawn by taking the tensile Stress at a certain point on a line segment which is perpendicular to the upper boundary and the lower boundary in the tensile Stress layer and has upper and lower end points respectively on the upper boundary and the lower boundary as a Y axis and the distance between the corresponding point and the upper boundary as an X axis is taken as a tensile Stress curve, and the ratio of the fixed integral of the tensile Stress curve and the thickness of the tempered glass is taken as the tensile Stress linear density, namely the ratio of the sum of the tensile stresses of the tempered glass measured by an Orihara Surface Stress Meter, FSM6000LE Stress Meter to the thickness of the glass.
Static pressure destructive test method:
1) the sample size was: length × width × thickness is 50mm × 50mm × 0.7 mm;
2) the operation method comprises the following steps: the description of the obtuse stress release test method is provided in the fifth stage 2019 of automobile technology and materials published by Waila, Suwencheng, Neibao and the like in ISSN1003-8817 under the unified publication No. CN 22-1187/U.
The Vickers hardness, modulus of elasticity, compressive strength, dielectric constant, coefficient of expansion, density, viscosity, liquidus temperature, softening point temperature, transition point Tg temperature, visible light average transmittance, viscosity referred to herein are determined using methods common in the art.
The crystalline form of the shaped portion within the soda glass can be obtained by XRD analysis.
The raw material glass provided by the invention comprises the following elements in mole percentage: 3 to 11.5 percent of Na, 17 to 24 percent of Si, 5.6 to 10.5 percent of Al, 0.25 to 5 percent of Mg and 58 to 62 percent of O. Preferably, the raw material glass comprises the following elements in mol percentage: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg and 58.52 to 61.52 percent of O; wherein the ratio of the Na content to the Li content is 1-11.5. The content of Si is controlled by controlling the content of O in the raw material glass raw components and a certain functional relation, so that the glass network structure taking Si as a core is controlled, and the glass has a better complete network structure. The sodium glass has certain characteristics of low content of Li and small content of Li, and mainly aims to reduce the high-temperature viscosity of the glass, facilitate melting, optimize the glass structure, improve the elasticity of the glass and construct a good network structure. In a word, the components of the raw material glass designed by the invention can comprehensively improve the network quality of the raw material glass, further realize higher intrinsic strength of the glass, and improve the impact resistance and the compressive stress storage capacity of the raw material glass. In addition, the easily-formed thickness range of the raw material glass is 0.4-10.0mm, preferably 0.4-8mm, transparent, equal-thickness and large-size glass can be obtained through the float normal line production, the thicker glass can be applied to a front windshield, and the thinner glass can be applied to a side window.
In some embodiments, the raw glass comprises the following oxides: 6 to 18 percent of Na2O, SiO 60% or more29% or more of Al2O31 to 6% of Li2O, and MgO with the content of more than or equal to 1 percent. The raw material glass has a certain amount of Al2O3The wear resistance of the raw material glass is obviously improved; controlling Al2O3The content of more than or equal to 9 percent is beneficial to improving the network structure size and the network integrity of the glass, and can improve the storage capacity of the compressive stress formed by ion exchange. Incorporation of MgO and relatively small amounts of Li in glass2The O, Mg and Li ions have higher field strength, have an aggregation effect at low temperature, can greatly tamp the glass network and increase the elasticity of the glass under the condition that the glass network is relatively complete, so the anti-falling capability of the glass is increased, the two elements have a melting promoting effect at high temperature, the melting difficulty of the glass is reduced, the Li has higher crystallization inclination, and the glass is raw material glass mainly exchanging K-Na ions, so the introduction amount of the Li needs to be controlled.
The raw material glass of the above embodiment has an elastic modulus of 65 to 88.2GPa and a Vickers hardness of 490 to 592kgf/mm2And the brittleness is 57.5-72.3. Wherein,
the common product solves the problem of high strength, which is divided into impact resistance, drop resistance, probe resistance and roller resistance, and the patent aims to reduce the brittleness of the product to improve the safety and increase the comprehensive strength, wherein, the special example defines the brittleness formula,the Vickers hardness is introduced into the formula to represent the plastic deformation capability of the glass, and although the plastic deformation capability of the glass is lower, the Vickers hardness and the elastic modulus of the glass are controlled within a reasonable range, so that the brittleness of the glass can be effectively reduced.
The dielectric constant of the raw material glass in the above embodiment is 5.5 to 7.75 under the condition that the frequency is 1MHZ to 3.5 GHZ. The raw material glass has low dielectric constant and small electrostatic adsorption, so that the raw material glass does not influence microwave communication in high-speed motion.
The expansion coefficient of the raw material glass in the above embodiment is 57 x 10 under the temperature condition of 20-400 DEG C-7/℃～101×10-7V. C. The lower expansion coefficient does not generate larger deformation, stress and strain in a larger temperature range, thereby obviously improving the safety and the reliability of the glass. Therefore, when the application scene of the product is extremely cold and hot, the safety of the product is ensured by the small expansion size.
The density of the raw material glass in the embodiment is 2.38-2.52g/cm at the temperature of 20 DEG C3. The invention controls the density range of the raw material glass to be 2.38-2.52g/cm3The glass has smaller density and substantially larger atom packing density, thereby having relatively larger plastic deformation capacity, reducing the brittleness of the glass and increasing the toughness of the glass.
In the above examples, the temperature corresponding to the raw material glass with the viscosity of lg3(visc./(Poise)) is 1250 to 1493 ℃; the liquid line temperature is 1060-1300 ℃; the softening point temperature is 710-880 ℃; the Tg temperature of the transition point is 515-620 ℃. In the composition of the raw material glass, MgO and Li are controlled2The content of O is small, so that the viscosity of the glass at high temperature is directly influenced, and the soda-alumina-silica glass has good viscosity and temperature gradient change characteristics and has a great effect on large-size forming; the raw material glass has a lower softening point which is lower than that of the common high-aluminum raw material glass by more than 50 ℃, and is more suitable for hot-forming required by various complex shapes.
In the embodiment, the size of the raw material glass is increased by 0.05-0.1% after the ion exchange treatment. That is, the dimensional change of the raw material glass before and after the chemical strengthening treatment is not so large that it is easy to control.
In some embodiments, the raw glass further comprises, in mole percent, the following oxides: 0.5% -2% of ZrO2(ii) a Wherein Li2O content of 2% or more, SiO2The content of (A) is 62 to 75 percent, and Al2O39 to 17 percent of Na2Content of O and Li2The sum of the contents of O is 9 to 20 percent, and the content of MgO is 2 to 12 percent; and the total content of alkali metal oxides is greater than Al2O3Content of (A), Na2Content of O and Li2The ratio of the content of O is 1-9.
The raw material glass of the above embodiment has an elastic modulus of 65 to 77GPa, a dielectric constant of 5.59 to 7.58 at a frequency of 1MHZ to 3.5GHz, and a density at 20 ℃ of 2.387 to 2.495g/cm3. By adding appropriate amount of ZrO2While to Li2Content of O, SiO2Content of (C), Al2O3Further control of the content of (A) and Na2Content of O and Li2The control of the ratio of the content of O enables the density of the raw glass to reach a smaller value with the elastic modulus and the dielectric constant of the raw glass kept at good levels.
The raw material glass in the above embodiment has a viscosity of lg3(visc./(Poise)), a corresponding temperature of 1274 to 1493 ℃, a liquidus temperature of 1086 to 1300 ℃, and a softening point temperature of 726 to 876 ℃.
In some embodiments, the blending index theta of O and Si in the raw material glass is 0.35-1.10; more preferably, the blending index theta is 0.61-1.10; more preferably, the blending index θ is 0.71 to 1.10. Wherein the blending index
Wherein X is the ratio of the content of O to the content of Si in the raw material glass.
In some embodiments, the raw glass further comprises, for example, in mole percentThe following oxides: 1% -4% of B2O3(ii) a Wherein the total content of alkali metal oxide and Al2O3Difference of contents of (A) and (B)2O3The absolute value of the ratio of the contents of (a) is 1 or more.
In some embodiments, the starting glass comprises an amorphous portion and a plurality of shaped portions; the size of each shaping part is 5-100 nm; the average size of all of the shaped portions is less than 50 nm; the average size of all of the shaped portions is less than 30 nm. Preferably, the average size of all the fixed parts is 10-30 nm. Preferably, the shaped portion comprises nepheline and ZrO2One or more of cordierite, spinel, a solid solution of beta-quartz, petalite and lithium silicate.
In some embodiments, the raw glass comprises Al2O3The content of (a) is 9-15.5%, and the raw material glass also comprises the following oxides in percentage by mole: 0.5-2% of rare earth oxide and 0.5-4% of K2O, 0 to 7% of P2O5(ii) a Wherein the rare earth oxide at least comprises CeO2And CeO2The content of (A) is more than or equal to 0.5 percent; k2O、Na2O and Li2The sum of the contents of O is 1 to 20 percent.
The raw material glass of the above embodiment, wherein the raw material glass has an elastic modulus of 65.6 to 75.4GPa and a Vickers hardness of 510 to 592kgf/mm2The expansion coefficient of the raw material glass at the temperature of 20-400 ℃ is 60 multiplied by 10-7/℃～100.3×10-7The density at 20 ℃ is 2.39-2.491 g/cm3. By adding appropriate amount of rare earth oxide and reacting with K2O、Na2O and Li2The sum of the contents of O is controlled so that the density of the raw glass can be reduced while maintaining the elastic modulus, Vickers hardness, and expansion coefficient of the raw glass at good levels.
The raw material glass described in the above examples has a viscosity of lg3(visc./(Poise)), a temperature corresponding to 1299 to 1493 ℃, a liquidus temperature of 1112 to 1300 ℃, a softening point temperature of 745 to 876 ℃, and a transition point Tg temperature of 515 to 579 ℃.
The brittleness of the raw material glass in the above embodiment is 60 to 69.2. By adding appropriate amount of rare earth oxide and reacting with K2O、Na2O and Li2The sum of the contents of O is controlled, so that the brittleness of the raw material glass is stabilized at a reliable level.
In some embodiments, the raw glass is Na29-15.5% of O, Li2The content of O is 2-5%. Preferably, in the raw material glass, Na2The content of O is 11-15.5%.
The raw material glass described in the above examples has an elastic modulus of 67.2 to 75.4GPa, a brittleness of 60 to 68.5, a dielectric constant of 5.87 to 7.52 at a frequency of 1MHZ to 3.5GHZ, and an expansion coefficient of 71 x 10 at a temperature of 20 to 400 ℃-7/℃～100.3×10-7The density at 20 ℃ is 2.42-2.48 g/cm3(ii) a The corresponding temperature is 1330-1450 ℃ when the viscosity of the raw material glass is lg3(visc./(Poise)), the liquidus temperature is 1130-1255 ℃, and the softening point temperature is 745-850 ℃.
In some embodiments, the raw glass further comprises 0.01 to 0.25% S by mole percentage. Preferably, the raw material glass contains 0.01 to 0.22 mol% of S, and more preferably, the raw material glass contains 0.01 to 0.15 mol% of S.
The preparation method of the chemically strengthened glass provided by the invention is a process for preparing the chemically strengthened glass provided by the invention after the raw material glass provided by the invention is placed in a mixed salt bath for ion exchange.
The mixed salt bath contains at least three metal ions which are respectively K+、Na+、Li+Wherein, K is+The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na+The content of Li in the mixed salt bath is not less than 500ppm+The content of the salt in the mixed salt bath is 20-1000 ppm. Using said mixed salt bath to pass K+-Na+Ion is replaced byThe main chemical reaction forms CS less than 50 microns on the surface of the raw material glass, so that the impact strength of the glass can be improved, and the safety of the glass can be ensured. During ion exchange, K is introduced+、Na+、Li+Ternary ion whose main ion exchange reaction is foreign K+With Na in glass+Carrying out a displacement reaction; alkali metal ion K in salt bath+、Na+、Li+Can be exchanged with each other, and Na is introduced into the salt bath+And Li+To balance K+-Na+Ion exchange reaction, control of K+The speed and the degree of the raw material glass entering are used for controlling the size and the total amount of CS formed on the surface of the raw material glass, so that the overhigh internal stress CT is avoided, and the safety of the glass is reduced. Preferably, K+Molar amount of (A)>Na+Molar amount of (A)>Li+The molar amount of (c). Wherein due to Li+The activity of the ion is greatest, therefore Li+The mol content of the ions is set to be the lowest among the alkali metal ions; introduction of Li into salt bath+Another important reason for the lower ion content is the control of Na in the salt bath+Ion-displacing Li in glass+Additional CS is formed, resulting in excessive internal stress CT, reducing the safety of the glass. Further preferably, Na+Is less than 30%, even less than 25%, of the total molar amount of alkali metal ions. More preferably, Li in the mixed salt bath+The content of (B) is 20-600 ppm.
The ion exchange time is 3-12 hours, and the temperature of the mixed salt bath in the ion exchange process is kept at 390-500 ℃.
In some embodiments, the mixed salt bath comprises nitrate ion NO3 -，NO3 -The molar amount of (a) is more than 95% of the total molar amount of the anions; the mixed salt bath contains hydroxide ions OH-，OH-The molar amount of (a) is less than 2.5% of the total molar amount of anions; the mixed salt bath also comprises other anions: CO 23 2-Or/and PO4 3-. The effect of anions in the mixed salt bath cannot be ignored and is the basisThe invention has an important characteristic that different anions have different complexing abilities to cations and the generated compounds have different characteristics, and various anions are introduced into the salt bath, so that the salt bath has an adsorption and precipitation effect on ions released from glass in ion exchange, and toxic and side effects in the salt bath are avoided.
In some embodiments, the production method is a single ion exchange, that is, the production method is performed in such a way that the starting glass is chemically strengthened only once. Because the salt bath is a mixed salt bath, two ion exchanges of potassium-sodium ion exchange and sodium-lithium ion exchange are included in the single ion exchange process.
The chemically strengthened glass provided by the invention is obtained by chemically strengthening the raw material glass provided by the invention according to the preparation method provided by the invention. The detection analysis of the chemically strengthened glass by using the conventional detection means in the field can find that: the thickness of the compressive stress layer formed on the surface of the chemically strengthened glass through ion exchange is less than or equal to 50 mu m, and the surface compressive stress is more than or equal to 600 MPa; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has the tensile stress linear density of 20000-75000 Mpa/mm, the thickness of 0.4-10 mm, the Vickers hardness of more than 520HV, the average visible light transmittance of 90-92% and the temperature of 1300 ℃ or less when the viscosity is lg4 (visc./(Poise)). The chemical strengthened glass has higher surface compressive stress CS and lower tensile stress CT, which shows that the chemical strengthened glass with higher CS and lower CT can be effectively formed by effectively controlling the degree of ion exchange reaction through the quaternary ion exchange salt bath. The chemically strengthened glass retains the elasticity endowed by the unique component design of the corresponding raw material glass, and simultaneously obtains higher impact resistance and safety through ion exchange.
In some embodiments, the chemically strengthened glass has a surface compressive stress of 650 to 1100MPa, preferably 700 to 900 MPa.
In some embodiments, the chemically strengthened glass has a tensile stress linear density of 28000 MPa/mm to 58000MPa/mm, preferably 28000 MPa/mm to 50000 MPa/mm. .
In some embodiments, the depth of the ion exchange layer formed by ion exchange at the surface of the chemically strengthened glass is at least 20um greater than the depth of the compressive stress layer. The maximum depth DOI of alkali metal ions entering the chemically strengthened glass through ion exchange can be detected through an electronic probe or SEM + EDS, the maximum depth DOL of surface compressive stress, the maximum depth CS of surface compressive stress and the maximum depth CT of internal tensile stress can be detected through a waveguide optical surface stress instrument, wherein the value of DOI is far larger than that of DOL.
In some embodiments, the chemically strengthened glass has an expansion coefficient of 50 x 10 at a temperature of-100 to 100 DEG C-7/℃～100×10-7V. C. The application scene of the chemically strengthened glass is that when the chemically strengthened glass is extremely cold and hot, the small expansion size ensures the safety of the product.
In some embodiments, the area of the largest fragments formed by fracture of the chemically strengthened glass having a length by width by thickness dimension of 50mm by 0.7mm when tested in a hydrostatic destructive test is between 5% and 45% of the total area of the chemically strengthened glass being tested.
The chemically strengthened glass provided by the present invention can be used as cover glass for mobile electronic devices and touch enabled displays, and can also be used in displays (or as display articles) (e.g., billboards, points of sale systems, computers, navigation systems, etc.), building articles (walls, fixtures, panels, windows, etc.), transportation articles (e.g., in automotive applications, trains, airplanes, ships, etc.), appliances (e.g., washing machines, dryers, dishwashers, refrigerators, etc.), or any article that requires some resistance to breakage.
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described in detail. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 12
In examples 1 to 12, 12 different raw material glasses were provided, and the raw material glasses of examples 1 to 12 were all produced by float method using a commercially available product as a raw material. The raw material glass components in examples 1 to 12 are shown in tables 1 and 2.
TABLE 1
TABLE 2
| Components | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| SiO2(mol％) | 69.22％ | 72.30％ | 64.80％ | 60.20％ | 67.40％ | 66.16％ |
| Al2O3(mol％) | 12.03％ | 9.10％ | 9.50％ | 15.57％ | 12.80％ | 12.04％ |
| P2O5(mol％) | 0.30％ | |||||
| B2O3(mol％) | 0.70％ | 0.70％ | 1.50％ | 0.38％ | ||
| MgO(mol％) | 1.52％ | 3.00％ | 7.80％ | 4.80％ | 2.10％ | 2.37％ |
| Li2O(mol％) | 4.50％ | 3.80％ | 5.60％ | 3.05％ | 2.50％ | 5.60％ |
| Na2O(mol％) | 11.00％ | 10.10％ | 12.00％ | 15.58％ | 11.20％ | 10.70％ |
| K2O(mol％) | 0.10％ | 1.40％ | ||||
| ZnO(mol％) | 0.05％ | 0.03％ | ||||
| ZrO2(mol％) | 0.50％ | 2.00％ | 1.15％ | |||
| TiO2(mol％) | 0.05％ | |||||
| SnO2(mol％) | 0.83％ | 0.50％ | 0.24％ | |||
| Tm2O3(mol％) | 0.20％ | |||||
| CeO2(mol％) | 0.03％ | 0.50％ | 0.50％ | |||
| Total | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ |
| β | 2.444 | 2.658 | 2.143 | 5.108 | 4.480 | 1.911 |
In tables 1 and 2, β means Na2Content of O and Li2The ratio of the content of O.
The molar percentages of the elements contained in the raw material glasses of examples 1 to 12 were obtained by calculation and are shown in tables 3 and 4.
TABLE 3
TABLE 4
| Kind of element | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 |
| Si(mol％) | 21.37％ | 22.84％ | 20.82％ | 18.38％ | 20.64％ | 20.53％ |
| Al(mol％) | 7.43％ | 5.75％ | 6.11％ | 9.51％ | 7.84％ | 7.47％ |
| P(mol％) | 0.00％ | 0.00％ | 0.00％ | 0.18％ | 0.00％ | 0.00％ |
| B(mol％) | 0.43％ | 0.44％ | 0.00％ | 0.00％ | 0.92％ | 0.24％ |
| Mg(mol％) | 0.47％ | 0.95％ | 2.51％ | 1.47％ | 0.64％ | 0.74％ |
| Li(mol％) | 2.78％ | 2.40％ | 3.60％ | 1.86％ | 1.53％ | 3.48％ |
| Na(mol％) | 6.79％ | 6.38％ | 7.71％ | 9.51％ | 6.86％ | 6.64％ |
| K(mol％) | 0.06％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.87％ |
| Zn(mol％) | 0.02％ | 0.00％ | 0.01％ | 0.00％ | 0.00％ | 0.00％ |
| Zr(mol％) | 0.00％ | 0.16％ | 0.00％ | 0.00％ | 0.61％ | 0.36％ |
| Ti(mol％) | 0.02％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ |
| Sn(mol％) | 0.26％ | 0.16％ | 0.08％ | 0.00％ | 0.00％ | 0.00％ |
| Tm(mol％) | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.00％ | 0.12％ |
| Ce(mol％) | 0.00％ | 0.00％ | 0.01％ | 0.15％ | 0.15％ | 0.00％ |
| O(mol％) | 60.38％ | 60.93％ | 59.15％ | 58.94％ | 60.80％ | 59.56％ |
| total | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ | 100.00％ |
| θ | 83.17％ | 99.84％ | 81.63％ | 49.48％ | 71.64％ | 75.74％ |
In the case of tables 3 and 4,
wherein X is the ratio of the content of O to the content of Si.
It can be seen that the contents of the O element and the Si element in the raw material glasses of examples 1 to 12 have the following characteristics:
the ratio of the content of O to the content of Si is X, wherein X satisfies:
individual also satisfies:
individual also satisfies:
examples 13 to 28
In examples 13 to 28, 16 different raw material glasses were provided, and the raw material glasses of examples 13 to 28 were all produced by float method using a commercially available product as a raw material. The raw material glass components in examples 13 to 28 are shown in tables 5 to 7.
TABLE 5
TABLE 6
TABLE 7
In tables 5 to 7, β means Na2Content of O and Li2The ratio of the content of O; na (Na)2O+Li2O represents Na2Content of O and Li2Sum of the contents of O; r2O represents the total content of alkali metal oxides, i.e., Na2O、Li2O and K2The total content of O; (R)2O-Al2O3)/B2O3The ratio of the difference between the alkali metal oxide content and the alumina content to the boron oxide content is shown.
As can be seen, Na contained in the raw material glasses of examples 13 to 282O、Li2The content of O has the following characteristics: na (Na)2Content of O and Li2The sum of the contents of O is 9 to 20 percent, and Na2Content of O and Li2The ratio of the content of O is 1-9.
Total content of alkali Metal oxides, Al, in the base glasses of examples 13 to 282O3Content of (A) and B2O3Has the following characteristics: the total content of alkali metal oxide is greater than Al2O3And the total content of alkali metal oxidesAmount and Al2O3Difference of contents of (A) and (B)2O3The absolute value of the ratio of the contents of (a) is 1 or more.
Examples 29 to 47
In examples 29 to 47, 19 different raw material glasses were provided, and the raw material glasses of examples 29 to 47 were all produced by float line using a commercially available product as a raw material. The raw material glass components in examples 29 to 47 are shown in tables 8 to 10.
TABLE 8
TABLE 9
Watch 10
In tables 8 to 10, beta means Na2Content of O and Li2The ratio of the content of O; na (Na)2O+Li2O represents Na2Content of O and Li2Sum of the contents of O; r2O represents the total content of alkali metal oxides, i.e., Na2O、Li2O and K2The total content of O; (R)2O-Al2O3)/B2O3Expressing the ratio of the difference between the content of alkali metal oxide and the content of alumina to the content of boron oxide; REO represents the total content of rare earth oxides, i.e., CeO2And Tm2O3The total content of (a).
As can be seen, Na contained in the raw material glasses of examples 29 to 472O、Li2The content of O has the following characteristics: na (Na)2Content of O and Li2The sum of the contents of O is 9 to 20 percent, and Na2Content of O and Li2The ratio of the content of O is 1-9.
Total content of alkali Metal oxides, Al in the base glasses of examples 29 to 472O3Content of (A) and B2O3Has the following characteristics: the total content of alkali metal oxide is greater than Al2O31 to 20%, and the total content of alkali metal oxides and Al2O3Difference of contents of (A) and (B)2O3The absolute value of the ratio of the contents of (a) is 1 or more.
The content of the rare earth oxide in the raw material glass of examples 29 to 47 has the following characteristics: the rare earth oxide at least comprises CeO2And CeO2The content of (A) is more than or equal to 0.5 percent; the total content of the rare earth oxide is 0.5-2%.
The raw material glasses of examples 1 to 47 were examined for physicochemical properties using the examination methods mentioned above, and the results are shown in tables 11 to 18.
TABLE 11
TABLE 12
Watch 13
TABLE 14
Watch 15
TABLE 16
TABLE 17
Watch 18
The raw material glasses of examples 1 to 47 were analyzed for viscosity-temperature properties by calculation based on the Herbert formula, and the results are shown in Table 19 below.
Watch 19
TABLE 21
TABLE 22
TABLE 23
Watch 24
TABLE 25
Watch 26
Watch 27
Watch 28
Watch 29
| Viscosity range | Practice ofExample 41 | Example 42 | Example 43 | Example 44 |
| Melting temperature/. degree.C | 1914 | 1827 | 1866 | 1869 |
| Clear range/. degree.C | 1914～2086 | 1827～2000 | 1866～2032 | 1869～2042 |
| Melting temperature range/. degree.C | 1691～2221 | 1602～2138 | 1649～2163 | 1645～2178 |
| Drawing temperature/. degree.C | 1520 | 1433 | 1483 | 1474 |
| Liquid line temperature/. degree.C | 1278 | 1194 | 1247 | 1231 |
| Softening point Ts/. degree C | 861 | 788 | 840 | 816 |
| Working Range/. degree C | 835～1278 | 763～1194 | 815～1247 | 790～1231 |
| Softening point Ts range/. degree C | 824～869 | 752～796 | 804～848 | 779～824 |
| Temperature range of material property/deg.C | 799～1278 | 729～1194 | 780～1247 | 755～1231 |
| Expansion softening point Tf/. degree C | 693 | 627 | 676 | 649 |
| Transition point Tg/. degree.C | 632 | 568 | 616 | 589 |
| Annealing temperature/. degree.C | 627 | 563 | 611 | 584 |
| Transition point Tg/. degree.C | 624 | 561 | 609 | 581 |
| Transition Range/. degree.C | 607～660 | 545～595 | 592～644 | 564～617 |
| Annealing Range/. degree.C | 607～645 | 545～581 | 592～630 | 564～602 |
| Annealing Range/. degree.C | 594～632 | 532～568 | 579～616 | 551～589 |
| Strain point/. degree C | 594～596 | 532～534 | 579～581 | 551～553 |
Watch 30
The viscosity-temperature properties of the base glasses of examples 1 to 47 were analyzed by calculation based on the fluent formula, and the results are shown in table 31 below.
Watch 31
Watch 32
Watch 33
Watch 34
Watch 35
Watch 36
Watch 37
Watch 38
Watch 39
Table 41
Watch 42
Examples 48 to 58
Examples 48 to 58 provide 11 mixed salt baths which can be used in the preparation process according to the invention. The components of the mixed salt bath provided in examples 48 to 58 and the amounts of solid alumina added are shown in tables 43 to 44.
Watch 43
Watch 44
In the mixed salt bath provided in examples 48 to 58, the amount of solid alumina added was 0.8% by mass or more of the mixed salt bath.
By computational analysis, it can be concluded that the contents of the respective ions per mole of the mixed salt bath in the mixed salt baths provided in examples 48 to 58 are shown in tables 45 and 46.
TABLE 45
TABLE 46
In the mixed salt bath provided in examples 48 to 58, K+Molar amount of (A)>Na+Molar amount of (A)>Li+The molar amount of (c).
Further analysis revealed that the percentages of each type of cation in the total amount of cations and the percentages of each type of anion in the total amount of anions in the mixed salt baths provided in examples 48 to 58 are shown in tables 47 and 48.
Watch 47
Watch 48
In the mixed salt bath provided in examples 48 to 58, K+Molar amount of (A)>Na+Molar amount of (A)>Li+Molar amount of (A), K+The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na+Is less than 30% (even less than 25%) of the total molar amount of alkali metal ions. NO3 -The molar amount of (A) is more than 95% of the total molar amount of anions, and OH-The molar amount of (a) is 2.5% or less of the total molar amount of anions.
Further analysis can lead to the concentrations of each type of cation in the mixed salt baths provided in examples 48 to 58 being shown in tables 49 and 50.
Watch 49
Watch 50
Examples 48 to 58 provide a mixed salt bath of Na+The content of Li in the mixed salt bath is not less than 500ppm+The content of Al in the mixed salt bath is 20-1000 ppm3+The content in the mixed salt bath is 2000ppm or less.
Examples 59 to 76
Examples 59-76 provide 18 chemically strengthened glasses according to the present invention. The raw materials for chemically strengthened glass provided in examples 59 to 76 and the parameters during the strengthening process are shown in tables 59 to 76.
Watch 51
Table 52
Watch 53
Watch 54
Watch 55
Watch 56
The chemical strengthening of examples 59-76 was examined using the above-mentioned examination method, and the results are shown in tables 57-59.
Watch 57
Watch 58
Watch 59
In tables 57-59, Dol _ K represents the depth of penetration of potassium ions in the salt bath into the glass, i.e., Dol corresponding to chemically strengthened glass; dol _ Na represents the depth of sodium ions in the salt bath penetrating into the glass, namely the DOI of the corresponding chemically strengthened glass.
To further illustrate that the ion exchange depth of layer (DOI) in the chemically strengthened glass provided by the present invention is at least 20um greater than the depth of layer of compressive stress (DOL). We also plot the DOI and DOL profiles within the chemically strengthened glass provided in example 75, see fig. 2, where the dashed curve is the DOI profile within the chemically strengthened glass provided in example 75 and the solid curve is the DOL profile within the chemically strengthened glass provided in example 75.
While embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than limiting, and many modifications may be made by those skilled in the art without departing from the spirit and the scope of the invention as defined by the appended claims.
Claims (19)
1. A chemically strengthened glass, characterized in that a compressive stress layer formed on the surface of the chemically strengthened glass by ion exchange has a thickness of one tenth or less of the thickness of the glass and a surface compressive stress of 600MPa or more; the compressive stress layer has a compressive stress curve, the compressive stress curve is a rounded curve extending from the surface of the chemically strengthened glass to a maximum depth of the compressive stress layer and having a gradually decreasing slope; the chemically strengthened glass has a tensile stress linear density of 20000 to 75000Mpa/mm, a thickness of 0.4 to 10mm, a Vickers hardness of more than 520HV, an average visible light transmittance of 90 to 92%, and a temperature of 1300 ℃ or less at a viscosity of lg4 (visc./(Poise)).
2. The chemically strengthened glass according to claim 1, wherein the surface compressive stress is 650 to 1100 MPa.
3. The chemically strengthened glass according to claim 2, wherein the surface compressive stress is 700 to 900 MPa.
4. The chemically strengthened glass according to claim 1, wherein the chemically strengthened glass has a tensile stress linear density of 28000 to 58000 Mpa/mm.
5. The chemically strengthened glass according to claim 36, wherein the chemically strengthened glass has a tensile stress linear density of 28000 to 50000 Mpa/mm.
6. The chemically strengthened glass according to claim 1, wherein a depth of an ion exchange layer formed by ion exchange on a surface of the chemically strengthened glass is at least 20 μm greater than the depth of the compressive stress layer.
7. The chemically strengthened glass according to claim 1, wherein the chemically strengthened glass has an expansion coefficient of 50 x 10 at a temperature of-100 to 100 ℃-7/℃～100×10-7/℃。
8. The chemically strengthened glass according to claim 1, wherein an area of a largest fragment formed by breaking of the chemically strengthened glass having a length x width x thickness dimension of 50mm x 0.7mm is 5% to 45% of a total area of the chemically strengthened glass under test, in a static pressure destructive test.
9. A method for preparing chemically strengthened glass is characterized in that raw material glass is placed in a mixed salt bath to carry out ion exchange to prepare the chemically strengthened glass according to the claims 1-8; the mixed salt bath contains at least three metal ions which are respectively K+、Na+、Li+Wherein, K is+The molar amount of (A) is more than 68% of the total molar amount of the metal ions, and Na+The content of Li in the mixed salt bath is not less than 500ppm+The content of the salt in the mixed salt bath is 20-1000 ppm.
10. The preparation method according to claim 9, wherein the preparation method is single-time ion exchange, the ion exchange time is 3-12 hours, and the ion exchange temperature is 390-500 ℃; in the mixed salt bath, Na+The molar amount of (a) is less than 30% of the total molar amount of alkali metal ions; the mixed salt bath contains nitrate ions NO3 -，NO3 -The molar amount of (a) is more than 95% of the total molar amount of the anions; the mixed salt bath contains hydroxide ions OH-，OH-The molar weight of the (B) accounts for 1.1 to 2.5 percent of the total molar weight of anions; li in the mixed salt bath+The content of (A) is 20-600 ppm; the mixed salt bath also comprises other anions: CO 23 2-Or/and PO4 3-。
11. A raw glass, characterized in that the raw glass is treated by the preparation method according to claims 9-10 to obtain the chemically strengthened glass according to claims 1-8, and the raw glass comprises the following elements in mol percent: 3.79 to 11.03 percent of Na, 17.62 to 23.67 percent of Si, 5.68 to 10.5 percent of Al, 0.01 to 3.79 percent of Li, 0.29 to 4.90 percent of Mg, 58.52 to 61.52 percent of O and Cl and S with the total of 0.01 to 0.25 percent; wherein the content of S is 0.01-0.22%, and the ratio of Na content to Li content is 1-11.5.
12. A raw material glass according to claim 11, comprising the following oxides in mol%: 6 to 18 percent of Na2O, SiO 60% or more29% or more of Al2O31 to 6% of Li2O, MgO of more than or equal to 1 percent and SO of 0.01 to 0.2 percent3。
13. A raw material glass according to claim 11, wherein the raw material glass has an elastic modulus of 65 to 88.2GPa and a Vickers hardness of490～592kgf/mm2The brittleness is 57.5-72.3; the dielectric constant of the raw material glass is 5.5-7.75 under the condition that the frequency is 1 MHZ-3.5 GHZ; the expansion coefficient of the raw material glass at the temperature of 20-400 ℃ is 57 multiplied by 10-7/℃～101×10-7/° c; the density of the raw material glass at the temperature of 20 ℃ is 2.38-2.52g/cm3(ii) a When the viscosity of the raw material glass is lg3(visc./(Poise)), the corresponding temperature is 1250-1493 ℃; the liquid line temperature is 1060-1300 ℃; the softening point temperature is 710-880 ℃; the Tg temperature of the transition point is 515-620 ℃.
14. A raw glass as defined in claim 11, further comprising the following oxides in mole percent: 0.5% -2% of ZrO21% -4% of B2O3(ii) a Wherein Li2O content of 2% or more, SiO2The content of (A) is 62 to 75 percent, and Al2O39 to 17 percent of Na2Content of O and Li2The sum of the contents of O is 9 to 20 percent, and the content of MgO is 2 to 12 percent; the total content of alkali metal oxide is greater than Al2O3The content of (A); total content of alkali metal oxide and Al2O3Difference of contents of (A) and (B)2O3The absolute value of the ratio of the contents of (a) is greater than or equal to 1; na (Na)2Content of O and Li2The ratio of the content of O is 1-9; the blending index theta of O and Si in the raw material glass is 0.35-1.10.
15. A raw material glass according to claim 14, wherein the raw material glass has an elastic modulus of 65 to 77GPa, a dielectric constant of 5.59 to 7.58 at a frequency of 1MHZ to 3.5GHZ, and a density at 20 ℃ of 2.387 to 2.495g/cm3(ii) a When the viscosity of the raw material glass is lg3(visc./(Poise)), the corresponding temperature is 1274-1493 ℃, the liquid line temperature is 1086-1300 ℃, and the softening point temperature is 726-876 ℃.
16. The raw material glass according to claim 14, which is characterized in thatCharacterized in that Al in the raw material glass2O3The content of (A) is 9% -15.5%; the raw material glass also comprises the following oxides in percentage by mole: 0.5-2% of rare earth oxide and 0.5-4% of K2O, 0 to 7% of P2O5(ii) a Wherein the rare earth oxide at least comprises CeO2And CeO2The content of (A) is more than or equal to 0.5 percent; k2O、Na2O and Li2The sum of the O content is 1 to 20 percent; the raw material glass has an elastic modulus of 65.6 to 75.4Gpa and a Vickers hardness of 510 to 592kgf/mm2The expansion coefficient of the raw material glass at the temperature of 20-400 ℃ is 60 multiplied by 10-7/℃～100.3×10-7The density at 20 ℃ is 2.39-2.491 g/cm3(ii) a When the viscosity of the raw material glass is lg3(visc./(Poise)), the corresponding temperature is 1299-1493 ℃, the liquidus temperature is 1112-1300 ℃, the softening point temperature is 745-876 ℃, and the transition point Tg temperature is 515-579 ℃; the brittleness of the raw material glass is 60-69.2.
17. A raw material glass according to claim 16, wherein in the raw material glass, Na29-15.5% of O, Li2The content of O is 2-5%; the elastic modulus of the raw material glass is 67.2-75.4 Gpa, the brittleness of the raw material glass is 60-68.5, the dielectric constant of the raw material glass under the condition that the frequency is 1 MHZ-3.5 GHZ is 5.87-7.52, and the expansion coefficient of the raw material glass under the temperature condition of 20-400 ℃ is 71 multiplied by 10-7/℃～100.3×10-7The density at 20 ℃ is 2.42-2.48 g/cm3(ii) a The corresponding temperature is 1330-1450 ℃ when the viscosity of the raw material glass is lg3(visc./(Poise)), the liquidus temperature is 1130-1255 ℃, and the softening point temperature is 745-850 ℃.
18. A raw material glass according to claim 16, wherein in the raw material glass, Na is contained in a molar percentage2The content of O is 11-15.5%, and Li2The content of O is 2-5%, and the raw material glass further comprises 0.01-0.25% of S.
19. A raw material glass as defined in claim 11, wherein the thickness of the raw material glass is 0.4-10 mm, and the size of the raw material glass after ion exchange treatment is increased by 0.05-0.1%; (ii) a The raw material glass comprises an amorphous part and a plurality of shaping parts; the size of each shaping part is 5-100 nm; the average size of all of the shaped portions is less than 50 nm; the average size of all the shaped portions is less than 30 nm; the average size of all the shaping parts is 10-30 nm; the shaped part comprises nepheline and ZrO2One or more of cordierite, spinel, a solid solution of beta-quartz, petalite and lithium silicate.
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